JP5178737B2 - Radiation-sensitive resin composition for spacer formation, spacer, spacer formation method, and liquid crystal display element - Google Patents

Description

  The present invention relates to a radiation-sensitive resin composition for forming a spacer, a spacer, a method for forming a spacer, and a liquid crystal display element.

  Conventionally, liquid crystal display devices are widely used in display devices that display high-quality images. A liquid crystal display device generally includes a liquid crystal layer capable of displaying an image with a predetermined orientation between a pair of substrates, and maintaining the distance between the substrates, that is, the thickness of the liquid crystal layer, is an element that determines image quality. For this purpose, a spacer for keeping the thickness of the liquid crystal layer constant is provided. The thickness between the substrates is generally referred to as “cell thickness”. The cell thickness usually indicates the thickness of the liquid crystal layer, in other words, the distance between two electrodes applying an electric field to the liquid crystal in the display region.

  Conventionally, the spacer has been formed by bead dispersion, but in recent years, a spacer with high positional accuracy has been formed by photolithography using a photosensitive composition. A spacer formed using such a photosensitive composition is called a photospacer.

  Radiation from a mercury lamp used as a light source in photolithography is usually around 436 nm (g-line), around 404 nm (h-line), around 365 nm (i-line), around 335 nm, around 315 nm (j-line), around 303 nm As a radiation sensitive polymerization initiator contained in the radiation sensitive resin composition, a compound having a maximum absorption wavelength in the wavelength region of these high spectrums is selectively used. It is normal. In most cases, from the viewpoint of transparency, a radiation-sensitive polymerization initiator having a maximum absorption wavelength in the region of i-line or less is used (see, for example, JP-A-2005-208360).

When a radiation-sensitive polymerization initiator having a maximum absorption wavelength near the g-line or h-line whose wavelength is longer than i-line is used, the radiation-sensitive polymerization initiator has absorption in a wavelength region close to visible light. The radiation sensitive resin composition containing the radiation polymerization initiator is colored, and the transparency of the formed film is lowered.
When the transparency of the film is low, the curing reaction proceeds on the film surface during exposure, while the curing reaction in the depth direction of the film becomes insufficient. As a result, the shape of the spacer obtained after development is inversely tapered (the cross-sectional shape is an inverted triangle whose side on the film surface is longer than the side on the substrate side), and the spacer peels off during the subsequent rubbing treatment of the alignment film It becomes.

On the other hand, when an spacer is formed by photolithography on a transparent substrate used in an actual spacer forming process, for example, a color filter, a proximity exposure machine is often used. In recent years, mercury lamps with high illuminance are generally used to improve the throughput of proximity exposure machines. In this case, although the throughput is improved, if a mercury lamp with high illuminance is used as it is, the life of the mirror used in the exposure machine is reduced, and therefore, high-energy short-wavelength radiation of less than 350 nm is cut by a filter. Often used. However, since most conventional radiation-sensitive polymerization initiators have a maximum absorption wavelength below 350 nm, cutting radiation with a wavelength of less than 350 nm will sufficiently provide active species such as radicals necessary for curing the radiation-sensitive resin composition. It cannot occur and the curing reaction becomes insufficient, and it becomes difficult to obtain satisfactory spacer dimensions and shapes.
In addition, since conventional radiation-sensitive polymerization initiators have poor liquid storage stability, handling problems that require the coating liquid to be stored in the cold, the resulting increase in cost, and on the glass substrate after coating There were problems such as stability over time.

  ADVANTAGE OF THE INVENTION According to this invention, the radiation sensitive resin composition for spacers which is highly sensitive and excellent in preservability is provided. It is another object of the present invention to provide a spacer formed using the radiation-sensitive resin composition, a method for forming the spacer, and a liquid crystal display device including the spacer.

Specific means for achieving the above object are as follows.
<1>
(A) a repeating unit having an alicyclic structure, a repeating unit having an acid group, a repeating unit having an arranged ethylenically unsaturated group via an ester group between the main chain, repeating units derived from styrene When a copolymer of chromatic also the least resin,
(B) a polymerizable unsaturated compound, and (C) (C1) hexaarylbiimidazole compound, (C2) aromatic mercapto compounds, and (C3) containing auxiliaries, in a sense a spacer formed radiation-sensitive resin composition There,
The ethylenically unsaturated group is a group introduced by adding a (meth) acrylate having an epoxy group to a repeating unit having an acidic group,
The radiation-sensitive resin composition for forming a spacer, wherein the alicyclic structure is a group derived from a monomer represented by the following general formula (3) .

In General Formula (3), X represents a divalent organic linking group, y represents 1 or 2, n represents an integer of 0 to 15, and R represents a hydrogen atom or a methyl group.
<2>
The radiation-sensitive resin composition for forming a spacer according to <1>, wherein the (C3) auxiliary agent contains at least one selected from a thioxanthone compound, a coumarin compound, a benzophenone compound, and an acridone compound.

<3>
The radiation-sensitive resin composition for spacer formation according to <1>, wherein the (C1) hexaarylbiimidazole compound is a compound represented by the following general formula (1) or general formula (2):

  In formula (1), X represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 9 carbon atoms; A represents a substituted or unsubstituted group having 1 to 12 carbon atoms An alkoxy group, or —COO—R (wherein R represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 9 carbon atoms); n is an integer of 1 to 3; An integer from 1 to 3;

Wherein ^{(2), X 1, X} 2 and ^{X 3} each independently represent a hydrogen atom, a halogen atom, a cyano group, and an alkyl group or an aryl group having a carbon number of 6 to 9 from 1 to 4 carbon atoms, ^{X 1} , X ² and X ³ do not simultaneously represent a hydrogen atom.

<4>
The radiation-sensitive resin composition for forming a spacer according to <1> , wherein the divalent organic linking group is one or a combination selected from an alkylene group, an arylene group, an ester group, an amide group, and an ether group.

<5>
Wherein (A) in the resin, but before the composition ratio of the repeating unit having a Kiabura ring (x) is 10 to 70 mol%, the composition ratio of the repeating unit having an acidic group (y) is 5 to 70 mol The spacer-forming radiation-sensitive resin composition according to <1>, wherein the composition ratio (z) of the repeating unit having an ethylenically unsaturated group is 10 to 70 mol%.

<6>
The radiation-sensitive resin composition for forming a spacer according to <1>, wherein a mass ratio [(B) / (A) ratio] of the polymerizable compound (B) to the resin (A) is 0.5 to 2.5. .

<7>
The spacer formed using the radiation sensitive resin composition for spacer formation as described in any one of said <1>- <6> .
<8>
Forming a photosensitive resin layer on a substrate using the radiation-sensitive resin composition for forming a spacer according to any one of <1> to <6> above;
Exposing at least a portion of the photosensitive resin layer to radiation that does not substantially contain a wavelength of less than 350 nm;
Developing the photosensitive resin layer after exposure;
Heating the photosensitive resin layer after development;
A method for forming a spacer comprising
<9>
The liquid crystal display element provided with the spacer as described in said <7> .

  ADVANTAGE OF THE INVENTION According to this invention, the radiation sensitive resin composition for spacers which was highly sensitive and excellent in preservability can be provided. Moreover, the spacer formed using the said composition, the formation method of this spacer, and the liquid crystal display element provided with this spacer can be provided.

  Hereinafter, the spacer-forming radiation-sensitive resin composition (hereinafter also simply referred to as “radiation-sensitive resin composition”), the spacer, the method for producing the spacer, and the liquid crystal display device of the present invention will be described in detail.

Feeling spacer for forming radiation-sensitive resin composition and a method for manufacturing a spacer for forming a radiation sensitive resin composition of the present invention the spacer comprises a repeating unit having a repeating unit, an acidic group having a (A) alicyclic structure in the main chain a repeating unit having an ethylenically unsaturated group disposed via an ester group between the resin is a copolymer of chromatic also reduced and the repeating unit derived from styrene,, (B) a polymerizable unsaturated compound, and (C) (C1) hexaarylbiimidazole compounds, containing (C2) aromatic mercapto compounds, and (C3) aid.
Since the radiation-sensitive resin composition for forming a spacer of the present invention has the above-described configuration, it has high sensitivity, excellent developability, and excellent storage stability. In particular, even at wavelengths that do not include wavelengths less than 350 nm, the sensitivity is high, the curing reaction is good, and the developability is excellent.
In addition, since the spacer produced from the radiation-sensitive resin composition is excellent in compressibility and has a high degree of deformation recovery, display unevenness in the display element and / or display device can be eliminated.

  The spacer manufacturing method of the present invention includes at least two substrates, a liquid crystal material disposed between the substrates, two electrodes for applying an electric field to the liquid crystal material, and a cell thickness between the substrates. A method for producing the spacer in a liquid crystal display device provided with a spacer to be regulated, wherein the radiation-sensitive resin composition layer (hereinafter referred to as the radiation-sensitive resin composition layer) containing the radiation-sensitive resin composition of the present invention on one of the two substrates. , Also referred to as “photosensitive resin layer”).

Layer formation process The layer formation process in this invention is a process of forming the photosensitive resin layer on the board | substrate using the radiation sensitive resin composition of this invention.
From this photosensitive resin layer, the spacer of the present invention is formed through other steps such as a patterning step, which will be described later, with good deformation recovery and capable of maintaining a uniform cell thickness. By using the spacer, display unevenness in an image in a liquid crystal display device in which display unevenness is likely to occur due to a change in cell thickness is effectively eliminated.

  Examples of methods for forming a photosensitive resin layer on a substrate include (a) a method of applying the radiation-sensitive resin composition of the present invention, and (b) a photosensitive transfer material having the photosensitive resin layer. And a transfer method in which the photosensitive resin layer is laminated and transferred by heating and / or pressing.

(A) Coating method The radiation-sensitive resin composition is coated by a known coating method such as spin coating, curtain coating, slit coating, dip coating, air knife coating, roller coating, or wire bar coating. , Gravure coating method, or extrusion coating method using a hopper described in US Pat. No. 2,681,294. Among them, JP 2004-89851 A, JP 2004-17043 A, JP 2003-170098 A, JP 2003-164787 A, JP 2003-10767 A, JP 2002-79163 A, A coating method using a slit nozzle or a slit coater described in JP-A No. 2001-310147 is suitable.

(B) Transfer method Transfer uses a photosensitive transfer material, and a photosensitive resin layer formed in a film shape on a temporary support is pressure-bonded to the surface of the support (or substrate) using a roller or a flat plate. Alternatively, after bonding by thermocompression bonding, the photosensitive resin layer is transferred onto the support by peeling off the temporary support. Specific examples include laminators and laminating methods described in JP-A-7-110575, JP-A-11-77942, JP-A-2000-334836, and JP-A-2002-148794. From the viewpoint of low foreign matter, it is preferable to use the method described in JP-A-7-110575.

In the case of forming the photosensitive resin layer, an oxygen blocking layer (hereinafter also referred to as “oxygen blocking film” or “intermediate layer”) can be further provided between the photosensitive resin layer and the temporary support. Thereby, the exposure sensitivity can be increased. Moreover, in order to improve transferability, you may provide the thermoplastic resin layer which has cushioning properties.
Regarding the temporary support, the oxygen-blocking layer, the thermoplastic resin layer, other layers constituting the photosensitive transfer material, and the method for producing the photosensitive transfer material, paragraph numbers [0024] to JP-A-2006-23696. The configuration and the manufacturing method described in [0030] can be applied.

  When the photosensitive resin layer is applied and formed by both the coating method (a) and the transfer method (b), the layer thickness is preferably 0.5 μm to 10.0 μm, and more preferably 1 μm to 6 μm. When the layer thickness is in the above range, the generation of pinholes during the formation of coating during production is prevented, and development and removal of unexposed portions can be performed without requiring a long time.

  Examples of the substrate on which the photosensitive resin layer is formed include a transparent substrate (for example, a glass substrate or a plastics substrate), a substrate with a transparent conductive film (for example, an ITO film), and a substrate with a color filter (also referred to as a color filter substrate). ), A driving substrate with a driving element (for example, a thin film transistor [TFT]), and the like. The thickness of the substrate is generally preferably 700 μm to 1200 μm.

Radiation sensitive resin composition Next, the radiation sensitive resin composition is demonstrated.
The radiation-sensitive resin composition of the present invention, (A) fat and repeating units having a ring structure, the repeating units and, arranged via an ester group between a main chain ethylenic unsaturated group having an acidic group a repeating unit having the resin is a copolymer of chromatic also reduced and the repeating unit derived from styrene, and (B) a polymerizable unsaturated compound, and (C) (C1) hexaarylbiimidazole compounds, (C2 ) Aromatic mercapto compound , and (C3) auxiliary agent.
Moreover, you may further contain another component as needed.

(A) Resin (A) resin, the repeating unit having a repeating unit having an alicyclic structure, a repeating unit having an acidic group, the disposed via an ester group between a main chain ethylenic unsaturated group When a copolymer of chromatic also reduced and the repeating unit derived from styrene, a.
Alicyclic structure that put the resin in the component (A), an acidic group and an ethylenically unsaturated group,, each may be contained in the different side chains, the same in at least two of these combined It may be contained in the side chain, or all may be contained in the same side chain.

  In the present specification, (meth) acryloyl group represents acryloyl group or methacryloyl group, (meth) acrylate represents acrylate or methacrylate, (meth) acryl represents acryl or methacryl, and (meth) acrylamide represents acrylamide. Alternatively, it represents methacrylamide, and (meth) acrylanilide represents acrylanilide or methacrylanilide.

Alicyclic structure
The alicyclic structure will be described.
(A) resin in the present invention, at least one including an alicyclic structure in the side chain.
A plurality of alicyclic structures may be contained in the same side chain of the resin (A). Also, cycloaliphatic structure, in the same side chain of the resin (A), the acidic group, an ethylenically unsaturated group may be contained together.
The front Kiabura ring structure, a main chain of the resin directly bonded to a main chain of (A), to only alicyclic structure may constitute the side chain of the resin (A), also resin (A) the bonded via a divalent organic linking group, it may constitute the side chain of the resin (a) as the group having an alicyclic structure.

When the resin (A) includes a branched structure in the side chain, examples of the branched structure include a branched alkyl group having 3 to 12 carbon atoms, such as an i-propyl group, i-butyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 2-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, i-amyl group, t-amyl group, Examples include 3-octyl group, t-octyl group, and the like, and groups having these. Among these, i-propyl group, s-butyl group, t-butyl group, isopentyl group and the like and groups having these are preferable, and i-propyl group, s-butyl group, t-butyl group and the like are further included. Groups are preferred.

  Examples of the alicyclic structure include an alicyclic hydrocarbon group having 5 to 20 carbon atoms, such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, an isobornyl group, and an adamantyl group. , Tricyclodecyl group, dicyclopentenyl group, dicyclopentanyl group, tricyclopentenyl group, tricyclopentanyl group and the like, and at least one selected from these groups. Among these, at least one selected from a cyclohexyl group, norbornyl group, isobornyl group, adamantyl group, tricyclopentenyl group, tricyclopentanyl group, dicyclopentenyl group, dicyclopentanyl group and the like and a group having these Further, at least one selected from a cyclohexyl group, an isobornyl group, a dicyclopentenyl group, a dicyclopentanyl group and the like and a group having these is preferable.

Examples of the divalent organic linking group include one or a combination selected from an alkylene group, an arylene group, an ester group, an amide group, and an ether group.
As an example of the said alkylene group, a C1-C20 alkylene group is mentioned preferably, More preferably, a C1-C10 alkylene group is preferable. Specific examples include methylene, ethylene, propylene, butylene, pentylene, hexylene, octylene, dodecylene, octadecylene, and the like, which may have a branched structure, a cyclic structure, or a functional group, and more preferably, Examples include a methylene group, an ethylene group, and an octylene group.
As an example of the said arylene group, a C6-C20 arylene group is mentioned preferably, More preferably, a C6-C12 arylene group is mentioned. Specific examples include a phenylene group, a biphenylene group, a naphthalene group, and an anthracene group, which may have a branched structure or a functional group, and more preferably a phenylene group or a biphenylene group.

When the resin (A) contains a branched structure in the side chain, monomers for introducing the branched structure into the side chain of the resin (A) include (meth) acrylates, vinyl ethers, vinyl esters. And (meth) acrylamides, (meth) acrylates, vinyl esters and (meth) acrylamides are preferred, and (meth) acrylates are more preferred. The tool body example, (meth) acrylic acid i- propyl, (meth) i- butyl acrylate, butyl (meth) s- acrylate, butyl (meth) t- acrylate, (meth) acrylic acid i- amyl, (Meth) acrylic acid t-amyl, (meth) acrylic acid sec-amyl, (meth) acrylic acid-iso-amyl, (meth) acrylic acid 2-octyl, (meth) acrylic acid 3-octyl, (meth) acrylic T-octyl acid etc. are mentioned, Among them, i-propyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl methacrylate and the like are preferable, and i-propyl methacrylate, methacrylic acid are more preferable. T-butyl acid and the like.

Monomer for introducing an alicyclic structure in the side chain of the resin (A) is a compound represented by the following general formula (3). Oite the general formula (3), X represents a divalent organic linking group, y represents 1 or 2, n represents an integer of 0 to 15, R represents a hydrogen atom or a methyl group.
Among general formulas (3) , y = 1 or 2, n = 0 to 4 is preferable, and n = 0 to 2 is more preferable.
The divalent organic linking group may have a substituent, and examples of the divalent organic linking group include one selected from an alkylene group, an arylene group, an ester group, an amide group, and an ether group. Or a combination is mentioned.
As an example of the said alkylene group, a C1-C20 alkylene group is mentioned preferably, More preferably, 1-10 are preferable. Specific examples include methylene, ethylene, propylene, butylene, pentylene, hexylene, octylene, dodecylene, octadecylene, and the like, which may have a branched structure, a cyclic structure, or a functional group, and more preferably, A methylene group, an ethylene group and an octylene group are preferred.
As an example of the said arylene group, the arylene group of 6-20 total carbon number is mentioned preferably, More preferably, the total carbon number 6-12 is preferable. Specific examples include a phenylene group, a biphenylene group, a naphthalene group, and an anthracene group, which may have a branched structure or a functional group, and more preferably a phenylene group or a biphenylene group.
Examples of the substituent that the divalent organic linking group may have include an alkyl group, a hydroxy group, an amino group, a halogen group, an aromatic ring group, and a group having an alicyclic structure.
The compound represented by the general formula (3) is preferable in terms of excellent developability and excellent deformation recovery rate. Specific examples thereof include the following compounds D-1 to D-3, D-5 to D-8, D -11, T-1 to T-4, T-9, and T-11 .

(A) As the monomer for introducing the alicyclic structure into the side chain of the resin, an appropriately produced monomer may be used, or a commercially available product may be used.
Examples of the commercially available products include FA-511A, FA-512A (S), FA-512M, FA-513A, FA-513M, TCPD-A, TCPD-M, H-TCPD-A, and H-TCPD-M. , TOE-A, TOE-M, H-TOE-A, H-TOE-M (all trade names, manufactured by Hitachi Chemical Co., Ltd.) and the like. Among these, FA-512A (S) and FA-512M are preferable because they are excellent in developability and excellent in the deformation recovery rate.

Acidic group (A) The resin contains at least one acidic group in the side chain.
A plurality of the acidic groups may be contained in the same side chain. Further, the acidic group may be included with the ethylenically unsaturated group attached through an alicyclic structure, and an ester group in the same side chain of the resin (A).
Further, the acidic group may be directly bonded to the main chain of the resin (A) to form a side chain of the resin (A) only with the acidic group, or a divalent organic linkage may be formed on the main chain of the resin (A). The side chain of the resin (A) may be formed as a group having an acidic group by bonding via a group. Here, as an example of the divalent organic linking group include a divalent organic linking groups exemplified in the description of the previous section Kiabura ring structure, preferred ranges are also the same.

  There is no restriction | limiting in particular as said acidic group, It can select suitably from well-known things. Examples thereof include a carboxyl group, a sulfonic acid group, a sulfonamide group, a phosphoric acid group, and a phenolic hydroxyl group. Among these, a carboxyl group and a phenolic hydroxyl group are preferable from the viewpoint of excellent developability and water resistance of the cured film.

  There is no restriction | limiting in particular as a monomer for introduce | transducing an acidic group into the side chain of said (A) resin, For example, (meth) acrylates, vinyl ethers, vinyl esters, (meth) acrylamides (Meth) acrylates, vinyl esters, and (meth) acrylamides are preferable, and (meth) acrylates are more preferable.

  Specific examples of the monomer for introducing an acidic group into the side chain of the (A) resin can be appropriately selected from known ones, such as (meth) acrylic acid, vinylbenzoic acid, malein Acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, sorbic acid, α-cyanocinnamic acid, acrylic acid dimer, addition reaction product of hydroxyl group-containing monomer and cyclic acid anhydride, ω-carboxy-polycaprolactone mono (meth) acrylate and the like. As these, those produced as appropriate may be used, or commercially available products may be used.

  Examples of the monomer having a hydroxyl group used in the addition reaction product of the monomer having a hydroxyl group and a cyclic acid anhydride include 2-hydroxyethyl (meth) acrylate. Examples of the cyclic acid anhydride include maleic anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride.

  As a monomer for introducing an acidic group into the side chain of the resin (A), commercially available products are manufactured by Toa Gosei Chemical Industry Co., Ltd .: Aronix M-5300, Aronix M-5400, Aronix M-5500, Aronix M-5600 (all trade names), Shin-Nakamura Chemical Co., Ltd .: NK ester CB-1, NK ester CBX-1 (all trade names), Kyoeisha Yushi Chemical Co., Ltd .: HOA-MP, HOA -MS (all trade names), Osaka Organic Chemical Industry Co., Ltd .: Viscoat # 2100 (trade name) and the like. Among these, (meth) acrylic acid and the like are preferable in terms of excellent developability and low cost.

Ethylenically unsaturated group The “ethylenically unsaturated group” bonded to the main chain via an ester group as the side chain of the resin (A) is not particularly limited, and examples thereof include (meth) acryloyl. Groups. The ester group (—COO—) connects the ethylenically unsaturated group and the (A) resin main chain.
In the present specification, the ethylenically unsaturated group bonded to the main chain via an ester group means that an atomic group containing the ethylenically unsaturated group is bonded to the main chain of the resin through an ester group. For this reason, the ester group is directly bonded to the main chain, but the ethylenically unsaturated group and the ester group may be directly bonded, or may be bonded via a linking group that connects the two. Also good.
In the present invention, a method for introducing an ethylenically unsaturated group in the side chain of the resin (A) is a way of adding the repeating units having an epoxy group (meth) acrylate having an acidic group. Manufacturing is easy, preferable because of low cost.

  The (meth) acrylate having an epoxy group is not particularly limited as long as it is a (meth) acrylate having an epoxy group. For example, in the compound represented by the following structural formula (1) and the following structural formula (2) The compounds represented are preferred.

In the structural formula (1), R ¹ represents a hydrogen atom or a methyl group. L ¹ represents an organic group.

In the structural formula (2), R ² represents a hydrogen atom or a methyl group. L ² represents an organic group. W represents a 4- to 7-membered aliphatic hydrocarbon group.

Of the compound represented by the structural formula (1) and the compound represented by the structural formula (2), the compound represented by the structural formula (1) is more preferable than the structural formula (2). In the structural formulas (1) and (2), it is more preferable that L ¹ and L ² are each independently an alkylene group having 1 to 4 carbon atoms.

  Although there is no restriction | limiting in particular as a compound represented by the said Structural formula (1) or a structural formula (2), For example, the following exemplary compounds (1)-(10) are mentioned.

Other monomers
The (A) resin has a repeating unit derived from styrene.
The (A) resin may contain other monomers and other groups may be introduced.
The other monomer is not particularly limited, for example, no alicyclic structure-containing (meth) acrylic acid ester, bi vinyl ether, a dibasic acid anhydride group, a vinyl ester group, a hydrocarbon alkenyl group And the like.
There is no restriction | limiting in particular as said vinyl ether group, For example, a butyl vinyl ether group etc. are mentioned.

The dibasic acid anhydride group is not particularly limited, and examples thereof include a maleic anhydride group and an itaconic anhydride group.
There is no restriction | limiting in particular as said vinyl ester group, For example, a vinyl acetate group etc. are mentioned.
There is no restriction | limiting in particular as said hydrocarbon alkenyl group, For example, a butadiene group, an isoprene group, etc. are mentioned.

  As content rate of the other monomer in said (A) resin, it is preferable that a composition ratio is 1-40 mass%, and it is more preferable that it is 2-30 mass%.

(A) As a specific example of resin, the compound (Exemplary compound P-52 and P-54 ) represented by the following structure is mentioned, for example.
In addition, x 1 , y 2 , z, and St in the exemplary compound represent the composition ratio (mass ratio) of each repeating unit, and a form that is configured in a preferable range described later is preferable. Moreover, the form comprised also in the preferable range mentioned later of the weight average molecular weight of each exemplary compound is suitable.

Synthesis Method (A) The resin can be synthesized from a two-stage process including a (co) polymerization reaction process of monomers and an ethylenically unsaturated group introduction process.
First, the (co) polymerization reaction includes (co) polymerization reactions of various monomers, and is not particularly limited and can be appropriately selected from known ones. For example, radical polymerization, cationic polymerization, anionic polymerization, coordination polymerization and the like can be appropriately selected for the active species of polymerization. Among these, radical polymerization is preferable from the viewpoint of easy synthesis and low cost. Moreover, there is no restriction | limiting in particular also about the polymerization method, It can select suitably from well-known methods. For example, a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, a solution polymerization method and the like can be appropriately selected. Among these, the solution polymerization method is more desirable.

Carbon number (A) As for the total carbon number of resin, 10 or more are preferable from a viewpoint of an elastic modulus (hardness). Especially, as for total carbon number, 10-30 are more preferable, Most preferably, it is 10-15.

Molecular Weight (A) The molecular weight of the resin is preferably 10,000 to 100,000 in terms of weight average molecular weight, more preferably 12,000 to 60,000, and particularly preferably 15,000 to 45,000. When the weight average molecular weight is within the above range, it is desirable from the viewpoint of suitability for producing a resin (preferably a copolymer) and developability. Moreover, it is preferable at the point which the shape formed by the fall of melt viscosity is hard to be crushed, the point which is hard to become a crosslinking failure, and the point which does not have the spacer shape residue in image development.
The weight average molecular weight is measured by gel permeation chromatography (GPC). GPC will be described in detail in the section of the examples described later.

Glass transition temperature (A) The glass transition temperature (Tg) of the resin is preferably 40 to 180 ° C, more preferably 45 to 140 ° C, and particularly preferably 50 to 130 ° C. When the glass transition temperature (Tg) is within the preferred range, a spacer having good developability and mechanical strength can be obtained.

Acid value (A) The preferred range of the acid value of the resin varies depending on the molecular structure that can be taken, but generally it is preferably 20 mgKOH / g or more, more preferably 40 mgKOH / g or more, and 50 to 130 mgKOH / g. Particularly preferred is g. When the acid value is within the preferred range, a spacer having good developability and mechanical strength can be obtained.

Tg
The resin (A) has a glass transition temperature (Tg) of 40 to 180 ° C. and a weight average molecular weight of 10,000 to 100,000 in that a spacer having good developability and mechanical strength can be obtained. It is preferable that the Tg is 45 to 140 ° C., the weight average molecular weight is 12,000 to 60,000, the Tg is 50 to 130 ° C., and the weight average molecular weight is 15, 000 to 45,000 is particularly preferable.
Furthermore, a preferable example of the (A) resin is more preferably a combination of the preferable molecular weight, glass transition temperature (Tg), and acid value.

(A) resin in the present invention, the alicyclic structure, an acidic group and mainly an ethylenically unsaturated bond disposed via an ester group between the chains, styrene and a separate repeating units (co Ru quaternary copolymerization more copolymers der having a polymerization unit). The copolymer is preferable from the viewpoint of deformation recovery rate, development residue, and reticulation when a pattern structure (for example, a color filter spacer) is formed.
Specifically, the resin (A) is a repeating unit having an alicyclic structure: ester between Y (y mol%), the main chain: a X (x mol%), the repeating unit having an acidic group Copolymerization of quaternary copolymerization or more having at least a repeating unit having an ethylenically unsaturated bond arranged through a group: Z (z mol%) and a repeating unit derived from styrene: St (St mol%) Ru united der. Furthermore, you may have other repeating units: L (1 mol%) as needed.
Such copolymers have, for example, a monomer having an alicyclic structure, a monomer having an acidic group, an ethylenically unsaturated bond disposed via an ester group between the main chain It can be obtained by copolymerizing a monomer, a monomer having styrene, and another monomer as required .

The copolymer composition ratio when the resin (A) is a copolymer is determined in consideration of the glass transition temperature and the acid value. Although it cannot be generally stated, the copolymer composition ratio can be in the following range.
In (A) resin, the composition ratio of the repeating unit having an alicyclic structure (x) is preferably from 10 to 70 mol%, more preferably 15 to 65 mol%, particularly preferably 20 to 60 mol%. When the composition ratio (x) is within the above range, good developability is obtained and the developer resistance of the image area is also good.
(A) As for the composition ratio (y) of the repeating unit which has an acidic group in resin, 5-70 mol% is preferable, 10-60 mol% is further more preferable, and 20-50 mol% is especially preferable. When the composition ratio (y) is within the above range, good curability and developability can be obtained.
(A) The composition ratio (z) of the repeating unit having “the ethylenically unsaturated bond arranged via the ester group between the main chain” in the resin is preferably 10 to 70 mol%, and preferably 20 to 70 mol. % Is more preferable, and 30 to 70 mol% is particularly preferable. When the composition ratio (z) is within the above range, the pigment dispersibility is excellent, the sensitivity and the polymerization curability are good, the liquid storage stability after preparation, and the dry film state after application are maintained for a long time. The stability over time is improved.
Furthermore, as (A) resin, composition ratio (x) is 10-70 mol%, composition ratio (y) is 5-70 mol%, and composition ratio (z) is 10-70 mol%. %, The composition ratio (x) is 15 to 65 mol%, the composition ratio (y) is 10 to 60 mol%, and the composition ratio (z) is 20 to 70 mol%. More preferably, the composition ratio (x) is 20 to 50 mol%, the composition ratio (y) is 20 to 50 mol%, and the composition ratio (z) is 30 to 70 mol%. Particularly preferred.

5-70 mass% is preferable with respect to the total solid of a composition, and, as for content in the photosensitive resin composition of said (A) resin, 10-50 mass% is more preferable.
Although (A) resin can be used together with the other resin mentioned later, the case where it consists only of said (A) resin is preferable.

Other Resins As examples of the resin that can be used in combination with the resin (A), compounds that swell to an alkaline aqueous solution are preferable, and compounds that are soluble in an alkaline aqueous solution are more preferable.
Suitable examples of the resin exhibiting swellability or solubility with respect to the alkaline aqueous solution include resins having an acidic group. Specific examples include a compound in which an ethylenically unsaturated double bond and an acidic group are introduced into an epoxy compound (for example, an epoxy acrylate compound), a vinyl copolymer having a (meth) acryloyl group and an acidic group in the side chain, and an epoxy. Examples thereof include a mixture of an acrylate compound and a vinyl copolymer having a (meth) acryloyl group and an acidic group in the side chain, and a maleamic acid-based copolymer.
The acidic group is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Among these, viewpoints such as availability of raw materials Therefore, a carboxyl group is preferably mentioned.

  When the photosensitive resin layer is formed on the substrate by a transfer method, it is particularly preferable to use the (A) resin and other resins in combination. In that case, as a total content (solid content) with resin which can be used together with (A) resin, 5 to 70 mass% is preferable with respect to the total solid content of the photosensitive resin layer, and 10 to 50 The mass% is more preferable. When the content is 5% by mass or more, the film strength of the photosensitive resin layer can be maintained, and the tackiness of the surface of the photosensitive resin layer can be maintained well. When the content is 70% by mass or less, the exposure sensitivity is good. become.

(B) Polymerizable unsaturated compound The photosensitive composition in this invention contains the (B) polymerizable unsaturated compound with the said (A) resin.
The polymerizable unsaturated compound can be selected and used from components constituting a known composition, for example, the components described in paragraphs [0010] to [0020] of JP-A-2006-23696, The components described in JP-A 2006-64921, paragraphs [0027] to [0053] can be mentioned.

  In the relationship with the (A) resin, the mass ratio [(B) / (A) ratio] of the (B) polymerizable compound to the (A) resin is preferably 0.5 to 2.5. It is more preferably 6 to 2.2, and particularly preferably 0.8 to 1.9. When the ratio (B) / (A) is within the above range, a spacer having good developability and mechanical strength can be obtained.

(C) Photopolymerization initiator (C1) Hexaarylbiimidazole compound The radiation-sensitive resin composition of the present invention contains at least (C1) hexaarylbiimidazole compound as component (C) in order to improve photosensitivity at long wavelengths. To do.
Examples of the hexaarylbiimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (2-chlorophenyl)- 4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) ) Biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2′-bis (2,4- Dichlorophenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′ 5,5′-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) ) Biimidazole, 2,2′-bis (2-cyanophenyl) -4,4 ′, 5.5′-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2′-bis (2-cyanophenyl) -4,4 ', 5,5'-tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2'-bis (2-methylphenyl) -4,4', 5,5'-tetrakis (4-methoxy) Carbonylphenyl) biimidazole, 2,2′-bis (2-methylphenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2′-bi (2-methylphenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2′-bis (2-ethylphenyl) -4,4 ′, 5,5 ′ -Tetrakis (4-methoxycarbonylphenyl) biimidazole, 2,2'-bis (2-ethylphenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2' -Bis (2-ethylphenyl) -4,4 ', 5,5'-tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2'-bis (2-phenylphenyl) -4,4', 5 5′-tetrakis (4-methoxycarbonylphenyl) biimidazole, 2,2′-bis (2-phenylphenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) bi Imidazole, 2,2′-bis (2-phenylphenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) biimidazole and the like;

2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-methoxyphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5 , 5′-tetrakis (3-methoxyphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (3,4-dimethoxyphenyl) biimidazole;

2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′ , 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2, 4,6-tribromophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4-dicyanophenyl) -4,4 ′, 5,5′-tetra Phenylbiimidazole, 2,2′-bis (2,4,6-tricyanophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4-dimethylphenyl) ) -4,4 ', 5,5'-tetraphenylbiimi Sol, 2,2′-bis (2,4,6-trimethylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4-diethylphenyl) -4 , 4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4,6-triethylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2 ′ -Bis (2,4-diphenylphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,4,6-triphenylphenyl) -4,4', 5 , 5′-tetraphenylbiimidazole, biimidazole compounds such as 2,2′-bis (2-fluorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, and the like.

Among these, as a particularly preferable compound, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole (trade name: B-CIM, manufactured by Hodogaya Chemical Co., Ltd.), 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra- (3,4-dimethoxyphenyl) biimidazole (trade name: HABI1311, manufactured by Nippon Sibel Hegner), 2,2′- Bis (2-methylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole (manufactured by Kurokin Kasei) is exemplified.
These may be used alone or in combination of two or more.

(C2) Aromatic Mercapto Compound The radiation-sensitive resin composition of the present invention contains (C2) an aromatic mercapto compound in order to increase spectral sensitivity.
Examples of the aromatic mercapto compound used in the radiation-sensitive resin composition of the present invention include compounds having a benzene ring or a heterocyclic ring as a mother nucleus and one or two mercapto groups. In the case of having two mercapto groups, one of the mercapto groups may be substituted with an alkyl group, an aralkyl group or a phenyl group, and takes the form of a dimer or disulfide via an alkylene group. Dimers may be used.
Among these, preferred examples of the aromatic mercapto compound include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, and N-phenylmercaptobenzimidazole. These may be used alone or in combination of two or more.

(C3) Auxiliary The radiation-sensitive resin composition of the present invention further contains (C3) an auxiliary to increase sensitivity.
The (C3) auxiliary agent is not particularly limited as long as it can increase the sensitivity, and among them, from the viewpoint of the effect of improving the sensitivity, from the thioxanthone compound, the coumarin compound, the benzophenone compound, and the acridone compound. It is preferable that at least one selected.

(C3-1) Thioxanthone Compound In the present specification, the thioxanthone compound means thioxanthone which may have a substituent.
Examples of the substituent include a linear or branched alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, and a halogen atom such as a fluorine atom, a chlorine atom or an iodine atom. Although there is no restriction | limiting in particular in the position of a substituent, Preferably it is 2-position and / or 4-position.

Specific examples of the thioxanthone compound include thioxanthone; 2-ethylthioxanthone, 2-propylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2, Examples include alkyl-substituted thioxanthones such as 4-methylethylthioxanthone; halogenated thioxanthones such as 2-chlorothioxanthone.
Of these, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, or 2-chlorothioxanthone is preferable.

(C3-2) Coumarin compound As a coumarin compound, the compound shown by general formula (I), (II) or (III) can be mentioned.

In general formula (I), R ¹ and R ² may be the same or different and are each independently a hydrogen atom, amino group, dialkylamino group, monoalkylamino group, N-substituted aminoalkyl group, halogen atom, or Represents an alkoxy group. Here, as an alkyl group and an alkoxy group, a C1-C4 thing is preferable.
In the general formula (II), ^{R 3} represents an alkylene group having 1 to 7 carbon atoms, preferably an alkylene group having from 1 to 4. R ⁴ and R ⁵ may be the same or different and each independently represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. When R ⁴ or R ⁵ represents an alkyl group, it preferably represents 1 to 4 alkyl groups.
In general formula (III), R ⁶ and R ⁷ may be the same or different, and each independently represents a hydrogen atom, an alkyl group having 1 to 7 carbon atoms (preferably 1 to 4 carbon atoms), or 1 to 1 carbon atoms. 4 represents an alkoxy group.

  Specific examples of coumarin compounds include 7-{{4-chloro-6- (diethylamino) -s-triazin-2-yl} amino} -3-phenylcoumarin, 7-{{4-methoxy- 6- (Diethylamino) -s-triazin-2-yl} amino} -3-phenylcoumarin, 7-{{4-methoxy-6- (diethylaminopropylamino) -s-triazin-2-yl} amino} -3 -Phenylcoumarin, N- (γ-dimethylaminopropyl) -N '-{3-phenylcoumarinyl- (7)} urea, 3-phenyl-7- (4'-methyl-5'-n-butoxy-benzotriazo -Lu-2-yl) coumarin and the like. Among these, 7-{{4-chloro-6- (diethylamino) -s-triazin-2-yl} amino} -3-phenylcoumarin is preferable.

  As said coumarin compound, the compound shown by the following general formula (VIII) which is a 3-aryl substituted coumarin compound can be mentioned.

In general formula (VIII), R ⁸ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 10 carbon atoms, preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, or a butyl group. It is. R ⁹ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a group represented by the following general formula (VIIIA), preferably a methyl group, an ethyl group, a propyl group, A butyl group or a group represented by the general formula (VIIIA), particularly preferably a group represented by the general formula (VIIIA).

R ¹⁰ and R ¹¹ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a haloalkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an optionally substituted 6 to 10 carbon atom. Represents an aryl group, an amino group, —N (R ¹⁶ ) (R ¹⁷ ), or a halogen atom. Here, examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, and an octyl group. Examples of the haloalkyl group having 1 to 8 carbon atoms include a chloromethyl group, a fluoromethyl group, and a trifluoromethyl group. Examples of the alkoxy group having 1 to 8 carbon atoms include a methoxy group, an ethoxy group, and a butoxy group. Examples of the aryl group having 6 to 10 carbon atoms that may be substituted include a phenyl group. Examples of the halogen atom include -Cl, -Br, and -F. Among these, a hydrogen atom, a methyl group, an ethyl group, a methoxy group, a phenyl group, or —N (R ¹⁶ ) (R ¹⁷ ) or —Cl is preferable.

R ¹² represents an optionally substituted aryl group having 6 to 16 carbon atoms, and specific examples include a phenyl group, a naphthyl group, a tolyl group, and a cumyl group. Examples of the substituent that can be introduced into the aryl group include an amino group, —N (R ¹⁶ ) (R ¹⁷ ), and an alkyl group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, and an octyl group). ), A haloalkyl group having 1 to 8 carbon atoms (for example, chloromethyl group, fluoromethyl group, trifluoromethyl group, etc.), an alkoxy group having 1 to 8 carbon atoms (for example, methoxy group, ethoxy group, butoxy group), hydroxy group, cyano Groups, halogens (eg -Cl, -Br, -F).
R ¹³ , R ¹⁴ , R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group or an octyl group). R ¹³ and R ¹⁴ may be bonded to each other to form a heterocyclic ring (for example, a piperidine ring, piperazine ring, morpholine ring, pyrazole ring, diazole ring, triazole ring, benzotriazole ring, etc.) together with the nitrogen atom. R ¹⁶ and R ¹⁷ may be bonded to each other to form a heterocyclic ring (for example, a piperidine ring, piperazine ring, morpholine ring, pyrazole ring, diazole ring, triazole ring, benzotriazole ring, etc.) together with the nitrogen atom. R ¹⁵ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, octyl group), an alkoxy group having 1 to 8 carbon atoms (for example, methoxy group, ethoxy group, butoxy group). ), An optionally substituted aryl group having 6 to 10 carbon atoms (for example, phenyl group), amino group, N (R ¹⁶ ) (R ¹⁷ ), and halogen (for example, —Cl, —Br, —F).

Zb represents = O, = S or = C (R ¹⁸ ) (R ¹⁹ ).
R ¹⁸ and R ¹⁹ each independently represent a cyano group, —COOR ²⁰ , or —COR ²¹ . R ²⁰ and R ²¹ are each independently an alkyl group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, octyl group), or a haloalkyl group having 1 to 8 carbon atoms (for example, chloromethyl group or fluoromethyl). Group, a trifluoromethyl group, etc.), an optionally substituted aryl group having 6 to 10 carbon atoms (for example, a phenyl group), and may be a heterocyclic ring or a benzene ring.
Moreover, the compound represented by the following general formula (IV) is mentioned as an example of another coumarin compound.

In the general formula (IV), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are each independently a hydrogen atom, amino group, dialkylamino group, monoalkylamino group, N-substituted amino group An alkyl group, a halogen, an alkyl group, or an alkoxy group is represented. Here, as an alkyl group and alkoxy, a C1-C4 thing is preferable. R ⁵ and R ⁶ may be bonded to each other to form a ring, and can also form a condensed ring with adjacent Z.
Z is preferably ═O, ═S, ═C (CN) ₂ , particularly preferably ═O.
Examples of the coumarin compound represented by the compound represented by the general formula (IV) include, for example, the following compounds 1 to 3 and NKX 1316, 1317, 1767, 1768, 1320 according to Hayashibara Biochemical Research Institute catalog. 1769, 1319, 1770, 1771, 846, 3502, 1619, which are also available as commercial products. Among these, NKX1767, 1768, 1619 (trade name: manufactured by Hayashibara Biochemical Laboratories) is preferable.

In the above compounds ^{1, R 1, R 2,} R 3 and ^{R 4} each independently represent a hydrogen atom or an alkyl group (preferably having 1 to 5 carbon atoms).

(C3-3) Benzophenone Compound Examples of the benzophenone compound include benzophenone, benzoylbenzoic acid, 4-phenylbenzophenone, 4,4-diethylaminobenzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 4-benzoyl-4 ′. -Methyldiphenyl sulfide etc. are mentioned.
(C3-4) Acridone Compound Examples of the acridone compound include compounds disclosed in JP-A-2007-41082, [0032] to [0042]. Among them, 10-n-butyl is a particularly preferable compound. -2-chloroacridone (trade name: NBCA, manufactured by Kurokin Kasei Co., Ltd.).

  The content of the component (C) in the radiation-sensitive resin composition of the present invention (that is, the total content of C1 to C3) is the total solid content of the radiation-sensitive resin composition (the total solid content of the photosensitive resin layer). ) To 0.5 to 25% by mass, and more preferably 0.5 to 15% by mass. When the content is within the above range, it is possible to prevent a decrease in photosensitivity and spacer strength, and it is possible to improve performance such as deformation recovery necessary as a spacer.

The radiation sensitive resin composition of this invention can contain other photoinitiators other than (C) component as needed. Examples of other photopolymerization initiators include aminoacetophenone compounds, acylphosphine oxide compounds, and oxime ester compounds.
Specific examples of the aminoacetophenone compound include IRGACURE (Irg) 369, IRGACURE (Irg) 379, IRGACURE (Irg) 907, etc. (all trade names; manufactured by Ciba Specialty Chemicals Co., Ltd.).
Specific examples of the acylphosphine oxide compound include DAROCUR TPO and Irgacure (Irg) 819 (all trade names; manufactured by Ciba Specialty Chemicals Co., Ltd.).
Specific examples of the oxime ester compound include IRGACURE (Irg) OXE01 and CGI242 (all trade names; manufactured by Ciba Specialty Chemicals Co., Ltd.).

Other components The photosensitive composition in the present invention contains at least the (A) resin, the (B) polymerizable unsaturated compound, and the (C) photopolymerization initiator, and, if necessary, other components. ((D) fine particles and the like) may be included.
As other components, it can be used by selecting from components constituting a known composition, for example, the components described in paragraph numbers [0010] to [0020] of JP-A-2006-23696, The components described in paragraph numbers [0027] to [0053] of 2006-64921 can be mentioned.

(D) Fine particles When the photosensitive resin layer is formed on the substrate by a transfer method, the photosensitive composition preferably contains fine particles.
(D) The fine particles are not particularly limited and may be appropriately selected depending on the purpose. For example, extender pigments described in JP-A-2003-302039 [0035] to [0041] are preferable, Colloidal silica is preferred from the viewpoint of obtaining a spacer having good developability and mechanical strength.

  The volume average particle diameter of the fine particles (D) is preferably 5 nm to 50 nm, more preferably 10 nm to 40 nm, and more preferably 15 nm to 30 nm in that a spacer having high mechanical strength is obtained. Particularly preferred.

  The content of the fine particles (D) in the photosensitive resin layer (that is, the spacer) is based on the total solid content (mass) in the photosensitive resin layer (spacer) from the viewpoint of obtaining a spacer having high mechanical strength. It is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and particularly preferably 15 to 30% by mass.

Exposure Step, Development Step, and Heating Step In the spacer manufacturing method of the present invention, a wavelength of less than 350 nm is applied to at least a part of the photosensitive resin layer (coating film) formed on the substrate after the layer formation step. It includes a step of exposing substantially free radiation (exposure step), a step of developing the exposed photosensitive resin layer (developing step), and a step of heating the photosensitive resin layer after development (heating step).
By the manufacturing method of the present invention, a spacer having an excellent deformation recovery rate can be produced.
The process of patterning by exposing and developing the photosensitive resin layer formed on the substrate may be referred to as a “patterning process”.
Examples of “radiation” in the present invention include ultraviolet rays, far ultraviolet rays, X-rays, electron beams, molecular beams, γ rays, synchrotron radiation, proton beam rays, and the like.

Exposure Step In the exposure step in the present invention, at least a part of the photosensitive resin layer (coating film) formed in the layer formation step is exposed to radiation that does not substantially contain a wavelength of less than 350 nm.
Here, “substantially does not include a wavelength of less than 350 nm” means that it can include a wavelength of less than 350 nm having an irradiation intensity that is substantially negligible compared to the irradiation intensity of a wavelength of 350 nm or more. means. That is, it may include a wavelength having an irradiation intensity that does not adversely affect the lifetime of the exposure machine mirror described later.
When exposing a part of the photosensitive resin layer, the exposure is performed through a predetermined pattern mask. In the present invention, it is possible to effectively suppress the life reduction of the mirror used in the exposure machine by cutting radiation having a short wavelength of less than 350 nm having high energy.
As the radiation used for the exposure, visible light, ultraviolet light, far ultraviolet light, or the like can be used.
Examples of the light source used for the light irradiation include medium to ultra high pressure mercury lamps, xenon lamps, metal halide lamps and the like.
Although it will not specifically limit if it is a radiation which does not contain the short wavelength less than 350 nm in wavelength, It is preferable to use what cut less than 350 nm from the radiation in the range of 190-450 nm.
The exposure dose of the radiation is usually 20 to 50, as a value obtained by measuring the intensity at the wavelength of the exposed radiation (for example, 365 nm) with an illuminometer (trade name: OAI model 356, manufactured by OAI Optical Associates Inc.). was 000J / ^{m 2,} it is preferable that 20~1500J / ^{m 2.}
The method for cutting the wavelength of the radiation of less than 350 nm is not particularly limited. For example, a method using a filter can be employed.
As the filter, for example, an ultraviolet transmission filter “UV-35” (trade name) manufactured by Toshiba Glass Co., Ltd. can be employed.

Development Step In the development step in the present invention, the exposed photosensitive resin layer (film) is developed.
As the developer used for the development treatment, a dilute aqueous solution of an alkaline substance may be used, but a solution obtained by adding a small amount of an organic solvent miscible with water to the dilute aqueous solution may also be used.
Prior to the development, it is preferable to spray pure water with a shower nozzle or the like to uniformly wet the surface of the photosensitive resin composition layer or the oxygen barrier layer.

  Examples of suitable alkaline substances include alkali metal hydroxides (eg, sodium hydroxide, potassium hydroxide), alkali metal carbonates (eg, sodium carbonate, potassium carbonate), alkali metal bicarbonates (eg, carbonate Sodium hydrogen, potassium hydrogen carbonate), alkali metal silicates (for example, sodium silicate, potassium silicate), alkali metal metasilicates (for example, sodium metasilicate, potassium metasilicate), triethanolamine, diethanolamine, monoethanol Examples include amines, morpholine, tetraalkylammonium hydroxides (for example, tetramethylammonium hydroxide), trisodium phosphate, and the like. The concentration of the alkaline substance is preferably 0.01 to 30% by mass, and the pH is preferably 8 to 14.

  Examples of the “water-miscible organic solvent” include, for example, methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n—. Preferable examples include butyl ether, benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, and N-methylpyrrolidone. It is done. The concentration of the water-miscible organic solvent in the developer is preferably from 0.1 to 30% by mass. Furthermore, a known surfactant may be added, and the concentration of the surfactant in the developer is preferably 0.01 to 10% by mass.

  The developer may be used as a bath solution or a spray solution. When removing the uncured portion of the photosensitive resin composition layer, methods such as rubbing the photosensitive resin composition layer with a rotating brush or a wet sponge in a developer can be combined. The liquid temperature of the developer is usually preferably from about room temperature (20 ° C.) to 40 ° C. The development time is usually about 10 seconds to 2 minutes, although depending on the composition of the photosensitive resin composition layer, the alkalinity and temperature of the developer, and the type and concentration when an organic solvent is added. If it is too short, the development of the non-cured part (non-exposed part in the case of negative type) may be insufficient, and if it is too long, the cured part (exposed part in the case of negative type) may also be etched. It is also possible to put a water washing step after the development processing. In this development step, the spacer is formed in a desired shape.

Heating Step In the heating step of the present invention, the pattern image (or spacer) made of the photosensitive resin layer obtained by the developing step is subjected to a heat treatment (also referred to as a baking treatment).
In the heat treatment, a pattern image (spacer pattern) formed by exposure and development is heated and cured. Thereby, the spacer of the present invention can be obtained.

  As a heat treatment method, various conventionally known methods can be used. For example, a method of storing a plurality of substrates in a cassette and processing them with a convection oven, a method of processing one by one with a hot plate, a method of processing with an infrared heater, and the like can be mentioned.

  The heating temperature in the heating step is usually 150 ° C. to 280 ° C., preferably 180 ° C. to 250 ° C. The heating time varies depending on the heating temperature, but when the baking temperature is 240 ° C., it is preferably 10 minutes to 120 minutes, more preferably 30 minutes to 90 minutes.

  In addition, in the method for producing a spacer, the spacer pattern formed by the exposure and development processes can prevent uneven film loss and prevent precipitation of components such as UV absorbers contained in the photosensitive resin layer. Therefore, post-exposure may be performed before the heating step. When post-exposure is performed before the heat treatment, it is possible to effectively prevent the minute foreign matters mixed during the lamination from expanding and causing defects.

Post exposure As a light source used for post exposure, any light source capable of irradiating light in a wavelength region capable of curing the photosensitive resin layer (for example, 365 nm or 405 nm) can be appropriately selected and used.
Specific examples include an ultra high pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, and the like.
Exposure may be any exposure to compensate for the exposure, usually at ^{50mJ / cm 2 ~5000mJ / cm 2} , preferably ^{200mJ / cm 2 ~2000mJ / cm 2} , more preferably 500 mJ ^/ cm 2 to 1000 mJ / Cm ² .

The spacer of the present invention can be formed after forming a color filter including a black shielding part such as a black matrix and a colored part such as a colored pixel.
The black shielding part, the colored part and the spacer are formed by arbitrarily combining a coating method for applying a photosensitive composition and a transfer method using a transfer material having a photosensitive resin layer made of the photosensitive composition. Is possible.
The black shielding part, the colored part, and the spacer can each be formed from a photosensitive composition. For example, after forming the photosensitive resin layer by directly applying the liquid photosensitive composition to the substrate, exposure and development are performed to form the black shielding portion and the colored portion in a pattern, A transfer material produced by forming the photosensitive resin layer by placing the liquid photosensitive composition on another substrate (temporary support) different from the substrate, and blocking the transfer material from the black shielding The spacer can be formed in a pattern by performing exposure and development after transferring the photosensitive resin layer in close contact with the substrate on which the portion and the colored portion are formed. In this manner, a color filter provided with a spacer can be manufactured.

Substrate for liquid crystal display device In the present invention, the substrate for liquid crystal display device comprises the spacer of the present invention. The spacer is preferably formed on a black light-shielding portion such as a black matrix formed on the support or on a driving element such as a TFT. Further, a transparent conductive layer (transparent electrode) such as ITO or a liquid crystal alignment film such as polyimide may exist between a black light shielding portion such as a black matrix or a driving element such as a TFT and a spacer.

For example, when the spacer is provided on the black light shielding portion or the driving element, the black light shielding portion (black matrix or the like) or the driving element previously disposed on the support is covered so that, for example, the photosensitive transfer material A photosensitive resin layer is laminated on the support surface, peeled and transferred to form a photosensitive resin layer, which is then subjected to exposure, development, heat treatment, etc. to form a spacer, thereby producing a substrate for a liquid crystal display device can do.
Similarly to the above, for example, after forming the photosensitive resin layer by directly applying the liquid photosensitive composition to the substrate, exposure and development are performed, and the black shielding portion and the coloring portion are formed into a pattern. Then, using a transfer material prepared by forming a photosensitive resin layer by placing the photosensitive composition of another liquid on another substrate (temporary support) different from the substrate, After the transfer material is brought into close contact with the substrate on which the black shielding portion and the colored portion are formed and the photosensitive resin layer is transferred, the spacer can be formed in a pattern by performing exposure and development. In this manner, a substrate for a liquid crystal display device provided with a spacer can be manufactured.
The liquid crystal display substrate may further be provided with colored pixels of three colors such as red (R), blue (B), and green (G) as necessary.

Liquid crystal display element In this invention, the liquid crystal display element can be comprised by providing the board | substrate for liquid crystal display devices. As one aspect of the liquid crystal display element, at least one of the pair of optically transparent supports (including the substrate for the liquid crystal display device of the present invention) and a liquid crystal layer and liquid crystal driving means (simple matrix drive) are provided between the supports. And an active matrix driving method).

  In this case, the substrate for a liquid crystal display device of the present invention can be used as a color filter substrate having a plurality of RGB pixel groups and pixels constituting the pixel group being separated from each other by a black matrix. Since this color filter substrate is provided with a high deformation recovery spacer having an excellent elastic recovery rate and weighted deformation amount, a liquid crystal display element including the color filter substrate is provided between the color filter substrate and the counter substrate. It is possible to effectively prevent display unevenness such as color unevenness due to uneven distribution of the liquid crystal material due to cell gap (cell thickness) variation, low temperature foaming, and the like. Thereby, the produced liquid crystal display element can display a vivid image.

  As another embodiment of the liquid crystal display element, at least one of the pair of light-transmissive supports (including the liquid crystal display device substrate of the present invention) and a liquid crystal layer and a liquid crystal driving means are provided between the supports. An element in which at least the liquid crystal driving means has an active element (for example, TFT) and the pair of substrates is regulated to a predetermined width by a highly deformable spacer having excellent elastic recovery rate and weight deformation amount. It is done. Also in this case, the substrate for a liquid crystal display device of the present invention can be used as a color filter substrate having a plurality of RGB pixel groups, and each pixel constituting the pixel group being separated from each other by a black matrix.

Examples of liquid crystals that can be used in the present invention include nematic liquid crystals, cholesteric liquid crystals, smectic liquid crystals, and ferroelectric liquid crystals.
In addition, the pixel group of the color filter substrate may be composed of two-color pixels exhibiting different colors, or may be composed of three-color pixels, four-color pixels or more. For example, in the case of three colors, it is composed of three hues of red (R), green (G), and blue (B). When arranging pixel groups of three colors of RGB, arrangement of mosaic type, triangle type, etc. is preferable, and when arranging pixel groups of four colors or more, any arrangement may be used. For producing the color filter substrate, for example, after forming a pixel group of two or more colors, the black matrix may be formed as described above, or conversely, the pixel group may be formed after forming the black matrix. Regarding the formation of RGB pixels, JP 2004-347831 A can be referred to.

Liquid crystal display device The liquid crystal display device includes the substrate for a liquid crystal display device. The liquid crystal display device includes the liquid crystal display element. That is, as described above, the space between the pair of substrates facing each other so as to face each other is regulated to a predetermined width by the spacer of the present invention, and the liquid crystal material is enclosed in the regulated gap (the enclosed part is called a liquid crystal layer). Thus, the thickness of the liquid crystal layer (cell thickness) is maintained at a desired uniform thickness.

Examples of liquid crystal display modes in the liquid crystal display device include STN type, TN type, GH type, ECB type, ferroelectric liquid crystal, antiferroelectric liquid crystal, VA type, IPS type, OCB type, ASM type, and various other types. A thing is mentioned suitably.
Among these, in the liquid crystal display device, from the viewpoint of exhibiting the effect of the present invention most effectively, a display mode in which display unevenness is likely to occur due to fluctuations in the cell thickness of the liquid crystal cell is desirable. Preferably, the mode, IPS type display mode, and OCB type display mode are configured.

  As an example of a configuration mode of a liquid crystal display device, (a) a driving side substrate in which driving elements such as thin film transistors (TFTs) and pixel electrodes (conductive layers) are arranged, and a counter electrode (conductive layer) provided with a counter electrode A substrate is disposed opposite to each other with a spacer interposed therebetween, and a liquid crystal material is sealed in the gap, and (b) a drive substrate and a counter substrate provided with a counter electrode (conductive layer) are interposed with a spacer. The liquid crystal material is disposed in the gap portion, and the like. The liquid crystal display device can be suitably applied to various liquid crystal display devices.

  The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, Industrial Research Committee, published in 1994)”. The liquid crystal display device is not particularly limited except that it includes the liquid crystal display element or the substrate for the liquid crystal display device of the present invention. For example, the liquid crystal display device may be configured as various types of liquid crystal display devices described in the “next-generation liquid crystal display technology”. be able to. In particular, it is effective in constructing a color TFT liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (Kyoritsu Publishing Co., Ltd., issued in 1996)”.

  The liquid crystal display device includes an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, a viewing angle compensation film, an antireflection film, a light diffusion film, except that it includes the above-described liquid crystal display device substrate or liquid crystal display element. It can be generally configured using various members such as an antiglare film. Regarding these members, for example, “'94 Liquid Crystal Display Peripheral Materials / Chemicals Market (Kentaro Shima, CMC Co., Ltd., published in 1994)”, “Current Status and Future Prospects of the 2003 Liquid Crystal Related Market (Part 2)” (Fuji Chimera Research Institute, Inc., 2003, etc.) ”.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “%” and “part” are based on mass.

Synthesis of Resin (A) A synthesis example of compound P-4 + St obtained by adding a structural unit derived from styrene to compound P-4 described above as an example of resin is shown below. However, the monomer ratio in the compound P-4 is changed from that shown above.

Synthesis example 1
7.48 parts of 1-methoxy-2-propanol (trade name: MFG, manufactured by Nippon Emulsifier Co., Ltd.) was added in advance to the reaction vessel, the temperature was raised to 90 ° C., and 3.1 parts of styrene (St; w), Tricyclopentenyl methacrylate (TCPD-M (trade name) manufactured by Hitachi Chemical Co., Ltd .; x) 4.28 parts, methacrylic acid (MAA; y) 11.7 parts, azo polymerization initiator (Wako Pure Chemical ( Co., Ltd., V-601 (trade name) 2.08 parts and 1-methoxy-2-propanol 55.2 parts in a 90 ° C. reaction vessel in a nitrogen gas atmosphere over 2 hours. It was dripped. After dripping, it was made to react for 4 hours and the acrylic resin solution was obtained.
Next, 0.15 part of hydroquinone monomethyl ether and 0.34 part of tetraethylammonium bromide were added to the acrylic resin solution, and then 26.4 parts of glycidyl methacrylate (GLM, manufactured by Tokyo Chemical Industry Co., Ltd.) was added for 2 hours. (GLM-MAA; z). After dripping, after reacting at 90 ° C. for 4 hours while blowing air, the solvent 1-methoxy-2-propyl acetate (MMPGAc, manufactured by Daicel Chemical Industries, Ltd.) was added so that the solid concentration was 45%. , A resin solution of an unsaturated group-containing compound P-4 + St ((A) resin) (solid content acid value: 76.0 mg KOH / g, Mw; 25,000, 1-methoxy-2-propanol / 1-methoxy-2 -Propyl acetate 45% solution) was obtained (x: y: z: St = 30 mol%: 27 mol%: 37 mol%: 6 mol%).
Here, GLM-MAA indicates a compound in which glycidyl methacrylate is bonded to methacrylic acid (the same applies hereinafter).
The molecular weight Mw of the compound P-4 + styrene compound (compound P-4 + St) indicates the weight average molecular weight, and the weight average molecular weight was measured by gel permeation chromatography (GPC method).
GPC uses HLC-8020GPC (manufactured by Tosoh Corporation), TSKgel, Super Multipore HZ-H (manufactured by Tosoh Corporation, 4.6 mm ID × 15 cm) as columns, and THF (tetrahydrofuran) as an eluent. ) Was used. The conditions were as follows: the sample concentration was 0.35 / min, the flow rate was 0.35 ml / min, the sample injection amount was 10 μl, the measurement temperature was 40 ° C., and an IR detector was used. In addition, the calibration curve is “standard sample TSK standard, polystyrene” manufactured by Tosoh Corporation: “F-40”, “F-20”, “F-4”, “F-1”, “A-5000”, It produced from eight samples of "A-2500", "A-1000", and "n-propylbenzene" (the same is true hereinafter).

  Hereinafter, (A) Synthesis examples for synthesizing the aforementioned compounds P-1 to P-4, P-9, P-10, P-25, P-53, and P-57 as other compounds of the resin, And Synthesis Examples (Synthesis Example 2 to Synthesis Example 8 and Synthesis Examples 10 to 11) for synthesizing compounds obtained by adding structural units derived from styrene to any of these compounds, and Synthesis Examples of Comparative Copolymers ( Synthesis example 9) is shown.

Synthesis example 2
The aforementioned compound P-4 was synthesized as follows. However, the monomer ratio in the compound P-4 is changed from that shown above.
In Synthesis Example 1, TCPD-M (x), methacrylic acid (y), and GLM were used so that x: y: z in compound P-4 was 34 mol%: 27 mol%: 39 mol% without using styrene. A resin solution (solid content acid value: 72) of compound P-4 ((A) resin) having an unsaturated group was synthesized by the same method as in Synthesis Example 1 except that the amount of -MAA (z) added was changed. 0.5 mg KOH / g, Mw; 22,000, 45% 1-methoxy-2-propanol / 1-methoxy-2-propyl acetate solution).

Synthesis example 3
Compound P-3 + St having a compound structure obtained by adding a structural unit derived from styrene to compound P-3 described above was synthesized as follows. However, the monomer ratio in the compound P-3 is changed from that shown above.
In Synthesis Example 1, tricyclopentenyl methacrylate was changed to cyclohexyl methacrylate (CHMA, manufactured by Tokyo Chemical Industry Co., Ltd.), and x: y: z: w in compound P-3 + St was 25 mol%: 25 mol%: 40 mol. %: The same method as in Synthesis Example 1 except that the addition amount of cyclohexyl methacrylate (x), methacrylic acid (y), GLM-MAA (z), and styrene (St) was changed so as to be 10 mol%. Resin solution of compound P-3 + St ((A) resin) having an unsaturated group (solid content acid value; 84.9 mg KOH / g, Mw; 26,000, 1-methoxy-2-propanol / 1- Methoxy-2-propyl acetate 45% solution) was obtained.

Synthesis example 4
Synthesis of the aforementioned compound P-3 was performed as follows. However, the monomer ratio in the compound P-3 is changed from that shown above.
In Synthesis Example 1, tricyclopentenyl methacrylate was changed to cyclohexyl methacrylate (CHMA, manufactured by Tokyo Chemical Industry Co., Ltd.) without using styrene, and x: y: z in compound P-3 was 32 mol%: 25 mol. %: Synthesized by the same method as in Synthesis Example 1 except that the amount of cyclohexyl methacrylate (x), methacrylic acid (y), and GLM-MAA (z) was changed so as to be 43 mol%. Resin solution of compound P-3 ((A) resin) having a saturated group (solid content acid value; 80.9 mgKOH / g, Mw; 21,000, 1-methoxy-2-propanol / 1-methoxy-2-propyl) A 45% acetate solution) was obtained.

Synthesis example 5
The aforementioned compound P-53 was synthesized as follows. However, the monomer ratio in Compound P-53 is changed from that previously shown.
In Synthesis Example 1, styrene was not used, and tricyclopentenyl methacrylate was changed to dicyclopentenyloxyethyl methacrylate (Hankuriru FA-512M (trade name) manufactured by Hitachi Chemical Co., Ltd.). The addition amounts of FA-512M (x), methacrylic acid (y), and GLM-MAA (z) were changed so that x: y: z was 46.2 mol%: 24.3 mol%: 29.5 mol%. Except for the above, a resin solution (solid content acid value; 70.2 mgKOH / g, Mw; 30,000) of compound P-53 having an unsaturated group ((A) resin) was synthesized by the same method as in Synthesis Example 1. 1-methoxy-2-propanol / 1-methoxy-2-propyl acetate 45% solution) was obtained.

Synthesis Example 6
Compound P-10 + St having a compound structure in which a structural unit derived from styrene was added to compound P-10 described above was synthesized as follows. However, the monomer ratio in Compound P-10 is changed from that shown above.
In Synthesis Example 1, tricyclopentenyl methacrylate was changed to dicyclopentanyl methacrylate (Hankuriru FA-513M (trade name) manufactured by Hitachi Chemical Co., Ltd.) and styrene was added to compound P-10. : The amount of FA-513M (x), methacrylic acid (y), GLM-MAA (z), and styrene was changed so that y: z: w was 25 mol%: 25 mol%: 40 mol%: 10 mol% The compound P-10 + St ((A) resin) having an unsaturated group was synthesized by the same method as in Synthesis Example 1 (solid acid value: 78.7 mgKOH / g, Mw; 28,000). 1-methoxy-2-propanol / 1-methoxy-2-propyl acetate 45% solution).

Synthesis example 7
The compound P-1 + St having a compound structure obtained by adding a structural unit derived from styrene to the compound P-1 described above was synthesized as follows. However, the monomer ratio in the compound P-1 is changed from that shown above.
In Synthesis Example 1, tricyclopentenyl methacrylate is changed to ADMA (manufactured by Idemitsu Kosan Co., Ltd.), and x: y: z: w in compound P-1 + St becomes 30 mol%: 24 mol%: 38 mol%: 8 mol%. Thus, compound P having an unsaturated group was synthesized by the same method as in Synthesis Example 1 except that the addition amount of ADMA (x), methacrylic acid (y), GLM-MAA (z), and styrene was changed. −1 + St ((A) resin) resin solution (solid content acid value: 74.1 mg KOH / g, Mw; 29,000, 1-methoxy-2-propanol / 1-methoxy-2-propyl acetate 45% solution) Obtained.

Synthesis Example 8
The compound P-2 + St having a compound structure obtained by adding a structural unit derived from styrene to the compound P-2 described above was synthesized as follows. However, the monomer ratio in the compound P-2 is changed from that shown above.
In Synthesis Example 1, tricyclopentenyl methacrylate was changed to isobornyl methacrylate (IBXMA, manufactured by Wako Pure Chemical Industries, Ltd.), and x: y: z: w in compound P-2 + St was 34 mol%: 24 mol%: 36 mol. %: Synthesized in the same manner as in Synthesis Example 1 except that the amounts of IBXMA (x), methacrylic acid (y), GLM-MAA (z), and styrene were changed so as to be 6 mol%. Resin solution (solid content acid value; 72.9 mg KOH / g, Mw; 29,000, 1-methoxy-2-propanol / 1-methoxy-2-propyl) of compound P-2 + St ((A) resin) having a saturated group A 45% acetate solution) was obtained.

Synthesis Example 9 (for comparison)
As a comparative resin, copolymer 1 was synthesized as follows.
In Synthesis Example 6, GLM-MAA was changed to glycidyl methacrylate (GLM; manufactured by Tokyo Chemical Industry Co., Ltd.), and x: y: z: w in copolymer 1 was 27 mol%: 25 mol%: 40 mol%: The compound was synthesized by the same method as in Synthesis Example 6 except that the addition amount of dicyclopentanyl methacrylate (x), methacrylic acid (y), GLM (z), and styrene was changed to 8 mol%. Resin solution of copolymer 1 having no saturated group (solid content acid value: 95.9 mg KOH / g, Mw; 18,000, 1-methoxy-2-propanol / 1-methoxy-2-propyl acetate 45% solution) Got.

Synthesis Example 10
Synthesis of the aforementioned compound P-57 was performed as follows.
In Synthesis Example 1, tricyclopentenyl methacrylate was changed to cyclohexyl methacrylate (CHMA, manufactured by Tokyo Chemical Industry Co., Ltd.), and x: y: z: MMA in compound P-57 was 40.1 mol%: 26. Except for changing the addition amount of cyclohexyl methacrylate (x), methacrylic acid (y), GLM-MAA (z), and methyl methacrylate (MMA) so as to be 6 mol%: 31.3 mol%: 2.0 mol% Was synthesized by the same method as in Synthesis Example 1, and a resin solution (solid content acid value: 97.6 mgKOH / g, Mw; 31,300, 1) of compound P-57 ((A) resin) having an unsaturated group. -Methoxy-2-propanol / 1-methoxy-2-propyl acetate 45% solution).

Synthesis Example 11
Synthesis of the aforementioned compound P-25 was performed as follows.
In Synthesis Example 1, tricyclopentenyl methacrylate was changed to cyclohexyl methacrylate (CHMA, manufactured by Tokyo Chemical Industry Co., Ltd.), and x: y: z: MMA in compound P-25 was 46.0 mol%: 20. Other than changing the addition amount of cyclohexyl methacrylate (x), methacrylic acid (y), GLM-MAA (z), and methyl methacrylate (MMA) so as to be 0 mol%: 32.0 mol%: 2.0 mol% Is synthesized by the same method as in Synthesis Example 1, and a resin solution (solid content acid value; 74.3 mgKOH / g, Mw; 33,600, 1) of compound P-25 ((A) resin) having an unsaturated group. -Methoxy-2-propanol / 1-methoxy-2-propyl acetate 45% solution).

Example 1: Coating method (method using liquid resist)
Production of Color Filter Substrate According to the method described in paragraph Nos. [0084] to [0095] of JP-A-2005-3861, a black matrix, an R (red) pixel, a G (green) pixel, and a B (blue) pixel are provided. A color filter was produced (hereinafter referred to as a color filter substrate). Here, the size of the color filter substrate was 400 mm × 300 mm.
Next, a transparent electrode of ITO (Indium Tin Oxide) was further formed on the R pixel, G pixel, B pixel and black matrix of the obtained color filter substrate by sputtering.

Formation of Photospacer A glass substrate coater MH-1600 having a slit-like nozzle on the ITO transparent electrode of the color filter substrate on which the ITO transparent electrode produced above is formed by sputtering (trade name; FAS Asia Co., Ltd.) The coating solution for photosensitive resin layer having the formulation shown in Table 1 below (Formulation 1, C1: C2: C3 = 3.7: 1: 1 (weight ratio) in Example 1) was applied by slit coating. did. Subsequently, using a vacuum dryer VCD (trade name; manufactured by Tokyo Ohka Kogyo Co., Ltd.), part of the solvent was dried for 30 seconds to eliminate the fluidity of the coating film, and then pre-baked on a 90 ° C. hot plate for 3 minutes. A photosensitive resin layer having a thickness of 5.2 μm was formed (layer forming step).

Subsequently, using a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp, a circular pattern mask (quartz exposure mask having an image pattern) having a diameter of 15 μm, and the mask and photosensitivity In a state where the color filter substrate placed so as to face the resin layer faces up in a substantially parallel and vertical state, the distance between the mask surface and the surface of the photosensitive resin layer is set to 100 μm, and through the mask at 365 nm Proximity exposure was performed for 10 seconds with ultraviolet light having passed through an ultraviolet transmission filter “UV-35” (trade name) manufactured by Toshiba Glass Co., Ltd. at an intensity (exposure amount) of 250 W / m ² .

  Next, a sodium carbonate-based developer (0.38 mol / liter sodium bicarbonate, 0.47 mol / liter sodium carbonate, 5% sodium dibutylnaphthalenesulfonate, an anionic surfactant, an antifoaming agent, and a stabilizer Containing the agent; trade name: T-CD1 (manufactured by Fuji Film Co., Ltd.) diluted 10-fold with pure water and shower developed at 29 ° C. for 30 seconds at a cone type nozzle pressure of 0.15 MPa. A pattern image was formed. Subsequently, a detergent (containing phosphate, silicate, nonionic surfactant, antifoaming agent, stabilizer; trade name: T-SD3 (Fuji Film Co., Ltd.)) was diluted 10 times with pure water. Using a liquid, sprayed with a shower at 33 ° C. for 20 seconds at a cone type nozzle pressure of 0.02 MPa to remove residues around the formed pattern image, and form a cylindrical spacer pattern with one spacer of 300 μm × 300 μm It formed so that it might become a space | interval (patterning process).

  Next, the color filter substrate provided with the spacer pattern was subjected to a heat treatment at 220 ° C. for 60 minutes (heat treatment step), thereby producing a photo spacer on the color filter substrate.

  Here, 1000 photo spacers obtained were measured for the highest position of the highest spacer from the glass substrate side using a three-dimensional surface structure analysis microscope (manufacturer: ZYGO Corporation, model: New View 5022) (n = 20) and the average value was defined as the height (average height). Moreover, the measurement of the bottom area of the obtained photospacer was performed using the SEM photograph. As a result, the photospacer had a cylindrical shape with a diameter of 15.1 μm and an average height of 4.7 μm.

Preparation of liquid crystal display device Separately, a glass substrate is prepared as a counter substrate, and the PVA mode patterning is performed on the transparent electrode and the counter substrate of the color filter substrate obtained as described above, and an orientation made of polyimide is further formed thereon. A membrane was provided.

  After that, a UV curable resin sealant is applied by a dispenser method at a position corresponding to the outer periphery of the black matrix provided so as to surround the pixel group of the color filter, and a liquid crystal for PVA mode is dropped and attached to the counter substrate. Combined. Thereafter, the bonded substrate was irradiated with UV, and then heat-treated to cure the sealing agent. A polarizing plate HLC2-2518 (trade name) manufactured by Sanlitz Co., Ltd. was attached to both surfaces of the liquid crystal cell thus obtained.

  Subsequently, FR1112H (trade name; chip type LED manufactured by Stanley Electric Co., Ltd.) as a red (R) LED, DG1112H (trade name; chip type LED manufactured by Stanley Electric Co., Ltd.) as a green (G) LED, blue ( B) DB1112H (trade name; chip-type LED manufactured by Stanley Electric Co., Ltd.) is used as the LED to form a sidelight type backlight, which is disposed on the back side of the liquid crystal cell provided with the polarizing plate. A liquid crystal display device was obtained.

Evaluation Deformation Recovery Rate The obtained photo spacer was measured and evaluated by a micro hardness meter (trade name: DUH-W201, manufactured by Shimadzu Corporation) as follows. The measurement was performed by a load-unloading test method using a frustum-shaped indenter with a diameter of 50 μm, a maximum load of 21 mN, and a holding time of 5 seconds. From this measured value, the deformation recovery rate [%] was obtained by the following formula and evaluated according to the following evaluation criteria. The measurement was performed in an environment of 22 ± 1 ° C. and 50% RH.
Deformation recovery rate (%)
= (Recovery amount after release of load [μm] / Deformation amount under load [μm]) × 100

Evaluation criteria 5: Deformation recovery rate was 90% or more.
4: The deformation recovery rate was 87% or more and less than 90%.
3: The deformation recovery rate was 85% or more and less than 87%.
2: Deformation recovery rate was 80% or more and less than 85%.
1: The deformation recovery rate was 75% or more and less than 80%.
0: Deformation recovery rate was less than 75%.

Elastic modulus at 15% compression at 25 ° C. In a room adjusted to a temperature of 25 ° C., the spacer has a height H ₁ [mm] corresponding to 85% of the initial height H ₀ [mm] at a load application speed of 10 mN / s. The load F ₁ [N] at the height H ₁ was read, and the elastic modulus at the time of 15% compression (strain amount = (H ₀ −H ₁ ) / H ₀ ) was calculated from the following formula. .
Elastic modulus = (load F ₁ / spacer bottom area S [mm ² ]) / strain amount

Developability In “Preparation of Photo Spacer”, after proximity exposure, development is performed in the same manner as the development conditions in each Example, and SEM observation is performed on the periphery of the formed photo spacer to confirm the presence of residues around the spacer. did.
Evaluation criteria 5: A residue was not seen at all.
4: Some residue was observed around the pattern.
3: Residue was observed around the pattern.
2: Residues were observed on the periphery of the pattern and on the substrate in the vicinity of the pattern.
1: Residue was confirmed in several places on the substrate.

Sensitivity Exposure and development treatment was performed under the same development conditions as above to determine whether or not a spacer pattern could be formed when the exposure amount was varied for the photosensitive resin layer coating solution used in each example, and SEM observation was performed. The minimum exposure amount capable of pattern formation was evaluated as sensitivity according to the following evaluation criteria.
Evaluation Criteria A: Pattern formation was possible with an exposure amount of less than 60 mJ / cm ² .
B: Pattern formation was possible with an exposure amount of 60 mJ / cm ² or more and less than 150 mJ / cm ² .
C: exposure of less than 150 mJ / cm ² or more 300 mJ / cm ² in the pattern formation is required.
D: An exposure amount of 300 mJ / cm ² or more was required for pattern formation.

Solution stability over time (storage stability)
After 180 days of natural aging (25 ° C.) of the coating solution for the photosensitive resin layer thus sealed and the photosensitive resin layer coating solution obtained by placing the photosensitive resin layer coating solution in a 60 ° C. oven for 2 weeks, the coating solution was used. The evaluation was performed according to the following criteria in the same manner as the sensitivity evaluation operation.
Evaluation Criteria A: Pattern formation was possible with an exposure amount of less than 60 mJ / cm ² .
B: Pattern formation was possible with an exposure amount of 60 mJ / cm ² or more and less than 150 mJ / cm ² .
C: exposure of less than 150 mJ / cm ² or more 300 mJ / cm ² in the pattern formation is required.
D: An exposure amount of 300 mJ / cm ² or more was required for pattern formation.

Examples 2-4 , 13, 14, Reference Examples 1-7, 8, 9, Comparative Examples 1-7
A liquid crystal display device was produced in the same manner as in Example 1 except that (A) the resin and (C) the photopolymerization initiator were changed as shown in Tables 1 to 3 in Example 1.
About the obtained liquid crystal display device, evaluation similar to Example 1 was performed (evaluation within the manufacturing process of a spacer (including developability)). The evaluation results are shown in Table 3. All the obtained spacers were cylindrical with a diameter of 15.1 μm and an average height of 4.7 μm.

Example 5 , Reference Examples 10 and 11 : Transfer Method In Example 1, the compound P-1 ((A) resin) used for the preparation of the coating solution for the photosensitive resin layer, fine particles, formation method, and the like are shown in Table 1 below. Formulas 2 and 4 (C1: C2: C3 = 1: 1.7: 1 (weight ratio)), and changed as shown in Table 3, instead of applying the coating solution for photosensitive resin layer, A photo spacer and a liquid crystal display device were produced in the same manner as in Example 1 except that the photosensitive resin layer was formed by performing transfer using the photosensitive transfer film for spacer shown. The obtained photospacer had a cylindrical shape with a diameter of 15.1 μm and an average height of 4.7 μm.

Production of Photosensitive Transfer Film for Spacer A polyethylene terephthalate film temporary support (PET temporary support) having a thickness of 75 μm was coated with a coating solution for a thermoplastic resin layer having the following formulation A and dried to obtain a dry layer thickness of 15. A 0 μm thermoplastic resin layer was formed.

Formulation A for Coating Solution for Thermoplastic Resin Layer
Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer 25.0 parts (= 55 / 11.7 / 4.5 / 28.8 [molar ratio], weight average molecular weight 90,000)
-Styrene / acrylic acid copolymer: 58.4 parts (= 63/37 [molar ratio], weight average molecular weight 8,000)
2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane
39.0 parts ・ Surfactant 1 shown below 10.0 parts methanol 90.0 parts 1-methoxy-2-propanol 51.0 parts methyl ethyl ketone 700 parts

* Surfactant 1
・ The following structure 1… 30%
・ Methyl ethyl ketone 70%

  Next, on the formed thermoplastic resin layer, an intermediate layer coating solution having the following formulation B was applied and dried to laminate an intermediate layer having a dry layer thickness of 1.5 μm.

Formulation B for coating solution for intermediate layer
Polyvinyl alcohol: 3.22 parts (Brand name: PVA-205 (saponification rate 80%), manufactured by Kuraray Co., Ltd.)
・ Polyvinylpyrrolidone: 1.49 parts (trade name: PVP K-30, manufactured by IS Japan Co., Ltd.)
・ Methanol: 42.3 parts ・ Distilled water: 524 parts

  Next, on the formed intermediate layer, a photosensitive resin layer coating solution ((A) resin is a compound in Table 3) having the formulation 2 shown in Table 1 below is further applied and dried to obtain a dry layer thickness of 5 A 2 μm photosensitive resin layer was laminated.

  As described above, after forming a laminated structure of PET temporary support / thermoplastic resin layer / intermediate layer / photosensitive resin layer (total thickness of three layers: 21.5 μm), the surface of the photosensitive resin layer is formed. Further, a polypropylene film having a thickness of 12 μm was applied as a cover film by heating and pressing to obtain a photosensitive transfer film for spacers.

Production of Photo Spacer A color filter substrate on which an ITO transparent electrode produced in the same manner as in Example 1 was formed by sputtering the cover film of the obtained photosensitive transfer film for spacer, and the exposed surface of the photosensitive resin layer was formed in the same manner as in Example 1. A laminator Lamic II type [trade name: manufactured by Hitachi Industries, Ltd.] is used to superimpose the film on an ITO transparent electrode, and the conveying speed is 2 m / min under a linear pressure of 100 N / cm at 130 ° C. under heating and heating conditions. Attach together. Thereafter, the PET temporary support was peeled and removed at the interface with the thermoplastic resin layer, and the photosensitive resin layer was transferred together with the thermoplastic resin layer and the intermediate layer (layer forming step).

Subsequently, using a proximity type exposure machine having an ultra-high pressure mercury lamp (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.), a mask having a circular pattern having a diameter of 15 μm (quartz exposure mask having an image pattern), the mask and thermoplasticity The distance between the mask surface and the surface of the photosensitive resin layer that is in contact with the intermediate layer of the photosensitive resin layer is set to 100 μm in a state where the color filter substrate arranged so as to face the resin layer is set up substantially in parallel and vertically, and the mask is From the thermoplastic resin layer side at an intensity (exposure amount) at 365 nm of 250 W / m ² , ultraviolet light transmitted through Toshiba Glass Co., Ltd. ultraviolet transmission filter “UV-35” (trade name) for 10 seconds, Proximity exposure.

Next, a triethanolamine developer (containing 30% triethanolamine, trade name: T-PD2 (manufactured by Fujifilm Corporation) 12 times with pure water (1 part of T-PD2 and 11 parts of pure water) The mixture was diluted with a ratio at a flat nozzle pressure of 0.04 MPa for 30 seconds at 30 ° C. to remove the thermoplastic resin layer and the intermediate layer. Subsequently, after air was blown off on the upper surface of the glass substrate, pure water was sprayed for 10 seconds by a shower, pure water shower cleaning was performed, and air was blown to reduce a liquid pool on the substrate.
Next, a sodium carbonate-based developer (0.38 mol / liter sodium bicarbonate, 0.47 mol / liter sodium carbonate, 5% sodium dibutylnaphthalenesulfonate, anionic surfactant, antifoaming agent, and stabilizer Trade name: T-CD1 (manufactured by Fuji Film Co., Ltd.) diluted 10 times with pure water) at 29 ° C. for 30 seconds at a cone type nozzle pressure of 0.15 MPa. An image was formed. Subsequently, a detergent (containing phosphate, silicate, nonionic surfactant, antifoaming agent, stabilizer; trade name: T-SD3 (Fuji Film Co., Ltd.)) was diluted 10 times with pure water. Using a liquid, sprayed with a shower at 33 ° C. for 20 seconds at a cone type nozzle pressure of 0.02 MPa to remove residues around the formed pattern image, and form a cylindrical spacer pattern with one spacer of 300 μm × 300 μm It formed so that it might become a space | interval (patterning process).
Next, the color filter substrate provided with the spacer pattern was subjected to a heat treatment at 220 ° C. for 60 minutes (heat treatment step), thereby producing a photo spacer on the color filter substrate. The obtained photospacer had a cylindrical shape with a diameter of 15.1 μm and an average height of 4.7 μm.
And the PVA mode liquid crystal display device was produced like Example 1 using the color filter board | substrate with which the photo spacer was produced.

Abbreviations of the compounds used in the above Examples and Comparative Examples are shown below.
B-CIM: 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole (manufactured by Hodogaya Chemical Co., Ltd.)
HABI1311: 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetrakis (3,4-dimethoxyphenyl) biimidazole (manufactured by Nippon Sibel Hegner)
・ Methylbiimidazole: 2,2′-bis (2-methyl) -4,4 ′, 5,5′-tetraphenylbiimidazole (manufactured by Kurokin Kasei Co., Ltd.)
IRG907: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (IRGACURE907, manufactured by Ciba Specialty Chemicals)
MBI: 2-mercaptobenzimidazole MBT: 2-mercaptobenzothiazole EAB: diethylaminobenzophenone NKX-1619: Coumarin compound (manufactured by Hayashibara Biochemical Research Institute)
MIBK-St: 30 wt% methyl isobutyl ketone dispersion of silica sol (Nissan Chemical)
NBCA: 10-n-butyl-2-chloroacridone (manufactured by Kurokin Kasei)
NPhMBI: N-phenylmercaptobenzimidazole

As is clear from Table 3, the radiation-sensitive resin compositions and spacers of the examples are superior in all evaluation items of sensitivity, deformation recovery rate, and liquid storage stability as compared with the comparative examples.

Claims (9)

(A) a repeating unit having an alicyclic structure , a repeating unit having an acidic group , a repeating unit having an ethylenically unsaturated group arranged via an ester group between the main chain, and a repeating unit derived from styrene When a copolymer of chromatic also the least resin,
A radiation-sensitive resin composition for forming a spacer, comprising (B) a polymerizable unsaturated compound, and (C) (C1) a hexaarylbiimidazole compound, (C2) an aromatic mercapto compound, and (C3) an auxiliary agent. There,
The ethylenically unsaturated group is a group introduced by adding a (meth) acrylate having an epoxy group to a repeating unit having an acidic group,
The radiation-sensitive resin composition for forming a spacer, wherein the alicyclic structure is a group derived from a monomer represented by the following general formula (3).
In General Formula (3), X represents a divalent organic linking group, y represents 1 or 2, n represents an integer of 0 to 15, and R represents a hydrogen atom or a methyl group.   The radiation-sensitive resin composition for forming a spacer according to claim 1, wherein the (C3) auxiliary agent contains at least one selected from a thioxanthone compound, a coumarin compound, a benzophenone compound, and an acridone compound. The radiation-sensitive resin composition for forming a spacer according to claim 1, wherein the (C1) hexaarylbiimidazole compound is a compound represented by the following general formula (1) or general formula (2):
In formula (1), X represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 9 carbon atoms; A represents a substituted or unsubstituted group having 1 to 12 carbon atoms An alkoxy group, or —COO—R (wherein R represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 9 carbon atoms); n is an integer of 1 to 3; An integer from 1 to 3;
Wherein ^{(2), X 1, X} 2 and ^{X 3} each independently represent a hydrogen atom, a halogen atom, a cyano group, and an alkyl group or an aryl group having a carbon number of 6 to 9 from 1 to 4 carbon atoms, ^{X 1} , X ² and X ³ do not simultaneously represent a hydrogen atom.   The radiation-sensitive resin composition for forming a spacer according to claim 1, wherein the divalent organic linking group is one or a combination selected from an alkylene group, an arylene group, an ester group, an amide group, and an ether group. The composition ratio (x) of the repeating unit having the alicyclic structure in the (A) resin is 10 to 70 mol%, and the composition ratio (y) of the repeating unit having the acidic group is 5 to 70 mol%. The spacer-forming radiation-sensitive resin composition according to claim 1, wherein the composition ratio (z) of the repeating unit having an ethylenically unsaturated group is 10 to 70 mol%.   2. The radiation-sensitive resin composition for forming a spacer according to claim 1, wherein a mass ratio [(B) / (A) ratio] of the polymerizable compound (B) to the resin (A) is 0.5 to 2.5. . The spacer formed using the radiation sensitive resin composition for spacer formation of any one of Claims 1-6 . Forming a photosensitive resin layer on a substrate using the radiation-sensitive resin composition for forming a spacer according to any one of claims 1 to 6 ;
Exposing at least a portion of the photosensitive resin layer to radiation that does not substantially contain a wavelength of less than 350 nm;
Developing the photosensitive resin layer after exposure;
Heating the photosensitive resin layer after development;
A method for producing a spacer comprising A liquid crystal display device comprising the spacer according to claim 7 .